WO2022018952A1 - Matériau d'électrolyte solide et batterie l'utilisant - Google Patents

Matériau d'électrolyte solide et batterie l'utilisant Download PDF

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WO2022018952A1
WO2022018952A1 PCT/JP2021/019273 JP2021019273W WO2022018952A1 WO 2022018952 A1 WO2022018952 A1 WO 2022018952A1 JP 2021019273 W JP2021019273 W JP 2021019273W WO 2022018952 A1 WO2022018952 A1 WO 2022018952A1
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solid electrolyte
electrolyte material
examples
material according
libr
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PCT/JP2021/019273
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English (en)
Japanese (ja)
Inventor
敬太 水野
敬 久保
哲也 浅野
武拓 田中
健介 若杉
知行 小森
貴裕 濱田
幹也 藤井
章裕 酒井
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パナソニックＩｐマネジメント株式会社
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Priority to EP21845617.6A priority Critical patent/EP4186862A4/fr
Priority to CN202180059452.5A priority patent/CN116133990A/zh
Priority to JP2022538605A priority patent/JPWO2022018952A1/ja
Publication of WO2022018952A1 publication Critical patent/WO2022018952A1/fr
Priority to US18/097,809 priority patent/US20230155170A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B9/00—Spraying apparatus for discharge of liquids or other fluent material, without essentially mixing with gas or vapour
    • B05B9/03—Spraying apparatus for discharge of liquids or other fluent material, without essentially mixing with gas or vapour characterised by means for supplying liquid or other fluent material
    • B05B9/04—Spraying apparatus for discharge of liquids or other fluent material, without essentially mixing with gas or vapour characterised by means for supplying liquid or other fluent material with pressurised or compressible container; with pump
    • B05B9/0403—Spraying apparatus for discharge of liquids or other fluent material, without essentially mixing with gas or vapour characterised by means for supplying liquid or other fluent material with pressurised or compressible container; with pump with pumps for liquids or other fluent material
    • B05B9/0413—Spraying apparatus for discharge of liquids or other fluent material, without essentially mixing with gas or vapour characterised by means for supplying liquid or other fluent material with pressurised or compressible container; with pump with pumps for liquids or other fluent material with reciprocating pumps, e.g. membrane pump, piston pump, bellow pump
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a solid electrolyte material and a battery using the same.
  • Patent Document 1 discloses an all-solid-state battery using a sulfide solid electrolyte.
  • An object of the present disclosure is to provide a novel solid electrolyte material having lithium ion conductivity.
  • the solid electrolyte material of the present disclosure is Consists of Li, M1, M2, and X M1 is one selected from the group consisting of Mg, Ca, Sr, Ba, and Zn. M2 is at least one selected from the group consisting of Gd and Sm. X is at least one selected from the group consisting of F, Cl, Br, and I.
  • the present disclosure provides a novel solid electrolyte material having lithium ion conductivity.
  • FIG. 1 shows a cross-sectional view of the battery 1000 according to the second embodiment.
  • FIG. 2 shows a schematic diagram of a pressure forming die 300 used for evaluating the ionic conductivity of a solid electrolyte material.
  • FIG. 3 is a graph showing a Core-Cole plot obtained by measuring the AC impedance of the solid electrolyte material of Example 1.
  • FIG. 4 is a graph showing the X-ray diffraction patterns of the solid electrolyte materials of Examples 1 to 9, 11, 12, 14 to 21, and 23 to 26.
  • FIG. 5 is a graph showing the X-ray diffraction patterns of the solid electrolyte materials of Examples 10, 13, and 22.
  • FIG. 6 is a graph showing the initial discharge characteristics of the battery of Example 1.
  • the solid electrolyte material according to the first embodiment comprises Li, M1, M2, and X.
  • M1 is one selected from the group consisting of Mg, Ca, Sr, Ba, and Zn.
  • M2 is at least one selected from the group consisting of Gd and Sm.
  • X is at least one selected from the group consisting of F, Cl, Br, and I.
  • the solid electrolyte material according to the first embodiment is a novel solid electrolyte material having lithium ion conductivity.
  • the solid electrolyte material according to the first embodiment may have an ionic conductivity of 5.0 ⁇ 10 -5 S / cm or more in the vicinity of room temperature, for example.
  • the solid electrolyte material according to the first embodiment can be used to obtain a battery having excellent charge / discharge characteristics.
  • An example of such a battery is an all-solid-state battery.
  • the all-solid-state battery may be a primary battery or a secondary battery.
  • the solid electrolyte material according to the first embodiment does not contain sulfur.
  • the sulfur-free solid electrolyte material is excellent in safety because it does not generate hydrogen sulfide even when exposed to the atmosphere.
  • the sulfide solid electrolyte disclosed in Patent Document 1 can generate hydrogen sulfide when exposed to the atmosphere.
  • the solid electrolyte material according to the first embodiment does not have to contain Y (yttrium).
  • the solid electrolyte material according to the first embodiment may contain an element that is inevitably mixed. Examples of such elements are hydrogen, oxygen, or nitrogen. Such elements may be present in the raw material powder of the solid electrolyte material or in the atmosphere for producing or storing the solid electrolyte material.
  • M1 may be one selected from the group consisting of Mg, Ca, and Zn.
  • X may be at least one selected from the group consisting of Cl and Br.
  • M1 may be Ca in order to further improve the ionic conductivity of the solid electrolyte material.
  • the solid electrolyte material according to the first embodiment may be a material represented by the following composition formula (1).
  • the following four formulas 0 ⁇ a ⁇ 0.5, 0 ⁇ b ⁇ 0.7, 0 ⁇ c ⁇ 4, and 1 ⁇ d ⁇ 1.25 Is satisfied.
  • the material represented by the composition formula (1) the ionic conductivity of the solid electrolyte material can be further improved.
  • the mathematical formula: b ⁇ 0.5 may be satisfied in the composition formula (1).
  • the mathematical formula: 0.025 ⁇ a ⁇ 0.2 may be satisfied in the composition formula (1).
  • the upper and lower limits of the range of a in the composition formula (1) are more than 0 (that is, 0 ⁇ a), 0.025, 0.05, 0.075, 0.1, 0.2, 0.25. , And any combination chosen from the numerical values of 0.5.
  • the upper limit value and the lower limit value of the range of b in the composition formula (1) may be defined by any combination selected from the numerical values of 0, 0.1, 0.3, 0.5, and 0.7.
  • the upper limit value and the lower limit value of the range of c in the composition formula (1) may be defined by any combination selected from the numerical values of 0, 3, and 4.
  • the upper limit value and the lower limit value of the range of d in the composition formula (1) may be defined by any combination selected from the numerical values of 1, 1.1, 1.2, and 1.25.
  • the X-ray diffraction pattern of the solid electrolyte material in the first embodiment is X by the ⁇ -2 ⁇ method using Cu—K ⁇ rays (wavelengths 1.5405 ⁇ and 1.5444 ⁇ , that is, wavelengths 0.15455 nm and 0.15444 nm). It can be obtained by linear diffraction measurement.
  • the obtained X-ray diffraction pattern at least two peaks exist in the range of the diffraction angle 2 ⁇ of 14.0 ° or more and 18.0 ° or less, and the diffraction angle of 29.0 ° or more and 32.0 ° or less. At least one peak may be present in the range of 2 ⁇ .
  • the crystal phase having these peaks is called the first crystal phase.
  • a path for lithium ions to diffuse in the crystal is likely to be formed. Therefore, the ionic conductivity of the solid electrolyte material is improved.
  • the first crystal phase is attributed to the trigonal crystal.
  • the "three-way crystal” in the present disclosure means a crystal phase having a crystal structure similar to that of Li 3 ErCl 6 disclosed in ICSD (Inorganic Crystal Structure Database) Collection Code 50151 and having an X-ray diffraction pattern peculiar to this structure. do.
  • "having a similar crystal structure” means that they are classified into the same space group and have similar atomic arrangement structures, and do not limit the lattice constant.
  • the solid electrolyte material X-ray diffraction pattern according to the first embodiment obtained by the X-ray diffraction measurement using Cu—K ⁇ ray at least one in the range of the diffraction angle 2 ⁇ of 12.0 ° or more and 16.0 ° or less. There may be a peak, and at least two peaks may be present in the range of the diffraction angle 2 ⁇ of 24.0 ° or more and 35.0 ° or less.
  • the crystal phase having these peaks is called the second crystal phase.
  • the solid electrolyte material containing the second crystal phase a path for lithium ions to diffuse in the crystal is likely to be formed. Therefore, the ionic conductivity of the solid electrolyte material is improved.
  • the second crystal phase is attributed to monoclinic crystals.
  • the "monoclinic crystal” in the present disclosure has a crystal structure similar to that of Li 3 ErBr 6 disclosed in ICSD (Inorganic Crystal Structure Database) Collection Code 50182, and has a crystal phase having an X-ray diffraction pattern peculiar to this structure. means.
  • the solid electrolyte material according to the first embodiment may further contain a third crystal phase different from the first crystal phase and the second crystal phase. That is, the solid electrolyte material according to the first embodiment may further contain a third crystal phase having a peak other than the above-mentioned range of the diffraction angle 2 ⁇ .
  • the third crystal phase may be interposed between the first crystal phase and the second crystal phase.
  • the third crystal phase may be attributed to, for example, an orthorhombic crystal.
  • Square crystal in the present disclosure means a crystal phase having a crystal structure similar to that of Li 3 YbCl 6 disclosed in ICSD (Inorganic Crystal Structure Database) Collection Code 50152 and having an X-ray diffraction pattern peculiar to this structure. do.
  • the solid electrolyte material according to the first embodiment may be crystalline or amorphous. Further, the solid electrolyte material according to the first embodiment may contain a mixture of crystalline and amorphous materials.
  • crystalline means that a peak is present in the X-ray diffraction pattern.
  • Amorphous means that a broad peak (that is, a halo) is present in the X-ray diffraction pattern. When amorphous and crystalline are mixed, peaks and halos are present in the X-ray diffraction pattern.
  • the first crystal phase that is, trigonal crystal
  • the second crystal phase that is, monoclinic crystal
  • the half-value full width of the diffraction peak having the highest intensity may be 0.30 ° or less.
  • the shape of the solid electrolyte material according to the first embodiment is not limited. Examples of such shapes are needle-shaped, spherical, or elliptical spherical.
  • the solid electrolyte material according to the first embodiment may be particles.
  • the solid electrolyte material according to the first embodiment may be formed to have the shape of a pellet or a plate.
  • the solid electrolyte material may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less.
  • the median diameter means the particle size when the cumulative volume in the volume-based particle size distribution is equal to 50%.
  • the volume-based particle size distribution is measured, for example, by a laser diffraction measuring device or an image analysis device.
  • the solid electrolyte material according to the first embodiment may have a median diameter of 0.5 ⁇ m or more and 10 ⁇ m or less. Thereby, the ionic conductivity of the solid electrolyte material according to the first embodiment can be further improved. Further, when the solid electrolyte material according to the first embodiment is mixed with another material such as an active material, the dispersed state of the solid electrolyte material and other materials according to the first embodiment becomes good.
  • the solid electrolyte material according to the first embodiment is produced, for example, by the following method.
  • Two or more halide raw material powders are mixed so as to have the desired composition.
  • the composition of the target solid electrolyte material is Li 2.8 Ca 0.1 Gd 0.9 Sm 0.1 Br 2 Cl 4.
  • the feedstock may be mixed in a pre-adjusted molar ratio to offset possible compositional changes in the synthetic process.
  • the mixture of raw material powders is fired in an atmosphere of an inert gas and reacted with each other to obtain a reactant.
  • the inert gas are helium, nitrogen, or argon. Firing may be performed in vacuum.
  • a mixture of raw material powders may be placed in a container (eg, a crucible and a vacuum sealed tube) and fired in a heating furnace.
  • the raw material powder may be mechanically reacted with each other in a mixing device such as a planetary ball mill to obtain a reactant. That is, the raw material powder may be mixed and reacted using the method of mechanochemical milling. The reactant thus obtained may be further calcined in an inert gas atmosphere or in vacuum.
  • the solid electrolyte material according to the first embodiment can be obtained.
  • the battery according to the second embodiment includes a positive electrode, a negative electrode, and an electrolyte layer.
  • the electrolyte layer is provided between the positive electrode and the negative electrode.
  • At least one selected from the group consisting of a positive electrode, an electrolyte layer, and a negative electrode contains the solid electrolyte material according to the first embodiment.
  • the battery according to the second embodiment contains the solid electrolyte material according to the first embodiment, it has excellent charge / discharge characteristics.
  • the battery may be an all-solid-state battery.
  • FIG. 1 shows a cross-sectional view of the battery 1000 according to the second embodiment.
  • the battery 1000 according to the second embodiment includes a positive electrode 201, an electrolyte layer 202, and a negative electrode 203.
  • the electrolyte layer 202 is provided between the positive electrode 201 and the negative electrode 203.
  • the positive electrode 201 contains positive electrode active material particles 204 and solid electrolyte particles 100.
  • the electrolyte layer 202 contains an electrolyte material.
  • the electrolyte material is, for example, a solid electrolyte material.
  • the negative electrode 203 contains negative electrode active material particles 205 and solid electrolyte particles 100.
  • the solid electrolyte particles 100 are particles made of the solid electrolyte material according to the first embodiment, or particles containing the solid electrolyte material according to the first embodiment as a main component.
  • the "particles containing the solid electrolyte material according to the first embodiment as a main component” mean the particles in which the component contained most in the molar ratio is the solid electrolyte material according to the first embodiment.
  • the solid electrolyte particles 100 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less. When it has a median diameter of 0.5 ⁇ m or more and 10 ⁇ m or less, the ionic conductivity of the solid electrolyte particles 100 can be further improved.
  • the positive electrode 201 contains a material capable of occluding and releasing metal ions (for example, lithium ions).
  • the material is, for example, a positive electrode active material (eg, positive electrode active material particles 204).
  • positive electrode active materials are lithium-containing transition metal oxides, transition metal fluorides, polyanionic materials, fluorinated polyanionic materials, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, or transition metal oxynitrides.
  • lithium-containing transition metal oxide is Li (Ni, Co, Al) O 2 or LiCoO 2.
  • the notation "(A, B, C)" in the chemical formula means "at least one selected from the group consisting of A, B, and C".
  • “(Ni, Co, Al)” is synonymous with “at least one selected from the group consisting of Ni, Co, and Al”.
  • the positive electrode active material particles 204 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less. When the positive electrode active material particles 204 have a median diameter of 0.1 ⁇ m or more, the dispersed state of the positive electrode active material particles 204 and the solid electrolyte particles 100 becomes good in the positive electrode 201. This improves the charge / discharge characteristics of the battery 1000. When the positive electrode active material particles 204 have a median diameter of 100 ⁇ m or less, the lithium diffusion rate in the positive electrode active material particles 204 is improved. As a result, the battery 1000 can operate at a high output.
  • the positive electrode active material particles 204 may have a median diameter larger than that of the solid electrolyte particles 100. As a result, in the positive electrode 201, the dispersed state of the positive electrode active material particles 204 and the solid electrolyte particles 100 becomes good.
  • the ratio of the volume of the positive electrode active material particles 204 to the total volume of the positive electrode active material particles 204 and the volume of the solid electrolyte particles 100 is 0.30 or more. It may be 0.95 or less.
  • the positive electrode 201 may have a thickness of 10 ⁇ m or more and 500 ⁇ m or less.
  • the electrolyte layer 202 contains an electrolyte material.
  • the electrolyte material is, for example, a solid electrolyte material according to the first embodiment.
  • the electrolyte layer 202 may be a solid electrolyte layer.
  • the electrolyte layer 202 may be composed of only the solid electrolyte material according to the first embodiment. Alternatively, the electrolyte layer 202 may be composed only of a solid electrolyte material different from the solid electrolyte material according to the first embodiment.
  • Examples of different solid electrolyte material and the solid electrolyte material according to the first embodiment Li 2 MgX '4, Li 2 FeX' 4, Li (Al, Ga, In) X '4, Li 3 (Al, Ga, In ) X '6, or LiI.
  • X' is at least one selected from the group consisting of F, Cl, Br, and I.
  • the solid electrolyte material different from the solid electrolyte material according to the first embodiment may be a solid electrolyte containing a halogen element, that is, a halide solid electrolyte.
  • the solid electrolyte material according to the first embodiment is referred to as a first solid electrolyte material.
  • the solid electrolyte material different from the solid electrolyte material according to the first embodiment is called a second solid electrolyte material.
  • the electrolyte layer 202 may contain not only the first solid electrolyte material but also the second solid electrolyte material. In the electrolyte layer 202, the first solid electrolyte material and the second solid electrolyte material may be uniformly dispersed. The layer made of the first solid electrolyte material and the layer made of the second solid electrolyte material may be laminated along the stacking direction of the battery 1000.
  • the electrolyte layer 202 may have a thickness of 1 ⁇ m or more and 1000 ⁇ m or less. When the electrolyte layer 202 has a thickness of 1 ⁇ m or more, the positive electrode 201 and the negative electrode 203 are less likely to be short-circuited. When the electrolyte layer 202 has a thickness of 1000 ⁇ m or less, the battery 1000 can operate at high output.
  • the negative electrode 203 contains a material that can occlude and release metal ions such as lithium ions.
  • the material is, for example, a negative electrode active material (eg, negative electrode active material particles 205).
  • Examples of negative electrode active materials are metal materials, carbon materials, oxides, nitrides, tin compounds, or silicon compounds.
  • the metal material may be a simple substance metal or an alloy.
  • Examples of metallic materials are lithium metals or lithium alloys.
  • Examples of carbon materials are natural graphite, coke, developing carbon, carbon fibers, spheroidal carbon, artificial graphite, or amorphous carbon. From the point of view of capacitance density, suitable examples of the negative electrode active material are silicon (ie, Si), tin (ie, Sn), a silicon compound, or a tin compound.
  • the negative electrode active material particles 205 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less. When the negative electrode active material particles 205 have a median diameter of 0.1 ⁇ m or more, the dispersed state of the negative electrode active material particles 205 and the solid electrolyte particles 100 becomes good in the negative electrode 203. This improves the charge / discharge characteristics of the battery 1000. When the negative electrode active material particles 205 have a median diameter of 100 ⁇ m or less, the lithium diffusion rate in the negative electrode active material particles 205 is improved. As a result, the battery 1000 can operate at a high output.
  • the negative electrode active material particles 205 may have a median diameter larger than that of the solid electrolyte particles 100. As a result, in the negative electrode 203, the dispersed state of the negative electrode active material particles 205 and the solid electrolyte particles 100 becomes good.
  • the ratio of the volume of the negative electrode active material particles 205 to the total volume of the negative electrode active material particles 205 and the volume of the solid electrolyte particles 100 in the negative electrode 203 is 0.30 or more. It may be 0.95 or less.
  • the negative electrode 203 may have a thickness of 10 ⁇ m or more and 500 ⁇ m or less.
  • At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 contains a second solid electrolyte material for the purpose of improving ionic conductivity, chemical stability, and electrochemical stability. You may be doing it.
  • the second solid electrolyte material may be a halide solid electrolyte.
  • halide solid electrolyte Li 2 MgX '4, Li 2 FeX' 4, Li (Al, Ga, In) X '4, Li 3 (Al, Ga, In) X' 6, or LiI.
  • X' is at least one selected from the group consisting of F, Cl, Br, and I.
  • the second solid electrolyte material may be a sulfide solid electrolyte.
  • solid sulfide electrolytes are Li 2 SP 2 S 5 , Li 2 S-Si S 2 , Li 2 SB 2 S 3 , Li 2 S-GeS 2 , Li 3.25 Ge 0.25 P 0.75 S 4 , or It is Li 10 GeP 2 S 12 .
  • the second solid electrolyte material may be an oxide solid electrolyte.
  • a solid oxide electrolyte is (I) NASION-type solid electrolytes such as LiTi 2 (PO 4 ) 3 or elemental substituents thereof, (Ii) A perovskite-type solid electrolyte such as (LaLi) TiO 3, (Iii) Lithium-type solid electrolytes such as Li 14 ZnGe 4 O 16 , Li 4 SiO 4 , LiGeO 4 or elemental substituents thereof, (Iv) a garnet-type solid electrolyte such as Li 7 La 3 Zr 2 O 12 or an elemental substituent thereof, or (v) Li 3 PO 4 or an N-substituted product thereof.
  • NASION-type solid electrolytes such as LiTi 2 (PO 4 ) 3 or elemental substituents thereof
  • a perovskite-type solid electrolyte such as (LaLi) TiO 3
  • Lithium-type solid electrolytes such as Li 14 ZnGe 4 O 16 , Li 4 SiO 4
  • the second solid electrolyte material may be an organic polymer solid electrolyte.
  • organic polymer solid electrolytes examples include polymer compounds and lithium salt compounds.
  • the polymer compound may have an ethylene oxide structure. Since the polymer compound having an ethylene oxide structure can contain a large amount of lithium salt, the ionic conductivity can be further improved.
  • lithium salt LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiSO 3 CF 3, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F 5) 2, LiN (SO 2 CF 3) (SO 2 C 4 F 9 ) or LiC (SO 2 CF 3 ) 3 .
  • One lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used.
  • At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 is a non-aqueous electrolyte solution, a gel electrolyte, or a gel electrolyte for the purpose of facilitating the transfer of lithium ions and improving the output characteristics of the battery 1000. It may contain an ionic liquid.
  • the non-aqueous electrolyte solution contains a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
  • non-aqueous solvent examples include a cyclic carbonate solvent, a chain carbonate solvent, a cyclic ether solvent, a chain ether solvent, a cyclic ester solvent, a chain ester solvent, or a fluorine solvent.
  • cyclic carbonate solvents are ethylene carbonate, propylene carbonate, or butylene carbonate.
  • chain carbonate solvents are dimethyl carbonate, ethylmethyl carbonate, or diethyl carbonate.
  • cyclic ether solvents are tetrahydrofuran, 1,4-dioxane, or 1,3-dioxolane.
  • chain ether solvents are 1,2-dimethoxyethane or 1,2-diethoxyethane.
  • An example of a cyclic ester solvent is ⁇ -butyrolactone.
  • An example of a chain ester solvent is methyl acetate.
  • fluorine solvents are fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, fluoroethylmethyl carbonate, or fluorodimethylene carbonate.
  • One non-aqueous solvent selected from these may be used alone. Alternatively, a mixture of two or more non-aqueous solvents selected from these may be used.
  • lithium salt LiPF 6, LiBF 4, LiSbF 6, LiAsF 6, LiSO 3 CF 3, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F 5) 2, LiN (SO 2 CF 3) (SO 2 C 4 F 9 ) or LiC (SO 2 CF 3 ) 3 .
  • One lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used.
  • the concentration of the lithium salt is, for example, 0.5 mol / liter or more and 2 mol / liter or less.
  • a polymer material impregnated with a non-aqueous electrolyte can be used.
  • polymer materials are polyethylene oxide, polyacrylic nitriles, polyvinylidene fluoride, polymethylmethacrylate, or polymers with ethylene oxide bonds.
  • cations contained in ionic liquids are (I) Aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium, (Ii) Aliphatic cyclic ammonium such as pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums, piperaziniums, or piperidiniums, or (iii) nitrogen-containing heteros such as pyridiniums or imidazoliums. It is a ring aromatic cation.
  • anion contained in the ionic liquid PF 6 -, BF 4 - , SbF 6 -, AsF 6 -, SO 3 CF 3 -, N (SO 2 CF 3) 2 -, N (SO 2 C 2 F 5 ) 2 -, N (SO 2 CF 3) (SO 2 C 4 F 9) -, or C (SO 2 CF 3) 3 - a.
  • the ionic liquid may contain a lithium salt.
  • At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a binder for the purpose of improving the adhesion between the particles.
  • binders are polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylic nitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, Polyacrylic acid hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polyacrylic acid ethyl ester, polyacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyether sulfone, hexafluoropolypropylene, styrene butadiene rubber , Or carboxymethyl cellulose.
  • Copolymers can also be used as binders.
  • binders are tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether and acrylic acid.
  • a copolymer of two or more materials selected from the group consisting of hexadiene Two or more mixtures selected from the above materials may be used as binders.
  • At least one selected from the positive electrode 201 and the negative electrode 203 may contain a conductive auxiliary agent in order to improve electron conductivity.
  • a conductive aid is (I) Graphites such as natural graphite or artificial graphite, (Ii) Carbon blacks such as acetylene black or ketjen black, (Iii) Conductive fibers such as carbon fibers or metal fibers, (Iv) Fluorocarbon, (V) Metal powders such as aluminum, (Vi) Conductive whiskers, such as zinc oxide or potassium titanate, (Vii) Conductive metal oxides such as titanium oxide, or (viii) Conductive polymer compounds such as polyaniline, polypyrrole, or polythiophene. Is. In order to reduce the cost, the conductive auxiliary agent (i) or (ii) described above may be used.
  • Examples of the shape of the battery 1000 according to the second embodiment are a coin type, a cylindrical type, a square type, a sheet type, a button type, a flat type, or a laminated type.
  • a material for forming a positive electrode, a material for forming an electrolyte layer, and a material for forming a negative electrode are prepared, and the positive electrode, the electrolyte layer, and the negative electrode are arranged in this order by a known method. It may be manufactured by making the arranged laminated body.
  • the solid electrolyte material in the examples is represented by the following composition formula (1).
  • Example 1> Preparation of solid electrolyte material
  • dry argon atmosphere LiBr, LiCl, CaBr 2 , GdCl 3 and SmCl 3 are used as raw material powders
  • LiBr: LiCl: CaBr 2 : GdCl 3 : SmCl 3 1.8: 1: 0.1: 0.9: 0.1 was prepared so as to have a molar ratio.
  • These raw powders were crushed and mixed in an agate mortar. The resulting mixture was placed in an alumina crucible and calcined in a dry argon atmosphere at 500 ° C.
  • the obtained calcined product was crushed in an agate mortar. In this way, the powder of the solid electrolyte material of Example 1 was obtained.
  • the solid electrolyte material of Example 1 had a composition represented by Li 2.8 Ca 0.1 Gd 0.9 Sm 0.1 Br 2 Cl 4.
  • the composition of the solid electrolyte material of Example 1, the values corresponding to a, b, c, and d of the composition formula (1), and the element species of M1 are shown in Table 1.
  • FIG. 2 shows a schematic diagram of a pressure molded die 300 used to evaluate the ionic conductivity of a solid electrolyte material.
  • the pressure forming die 300 was provided with a punch upper part 301, a frame type 302, and a punch lower part 303. Both the upper punch 301 and the lower punch 303 were made of electron-conducting stainless steel.
  • the frame 302 was made of insulating polycarbonate.
  • Example 1 Using the pressure-molded die 300 shown in FIG. 2, the ionic conductivity of the solid electrolyte material of Example 1 was evaluated by the following method.
  • the powder 101 of the solid electrolyte material of Example 1 was filled inside the pressure forming die 300. Inside the pressure forming die 300, a pressure of 360 MPa was applied to the powder 101 of the solid electrolyte material of Example 1 using the punch upper part 301 and the punch lower part 303.
  • the upper punch 301 and the lower punch 303 were connected to a potentiostat (Princeton Applied Research, VersaSTAT4) equipped with a frequency response analyzer.
  • the upper part 301 of the punch was connected to the working electrode and the terminal for measuring the potential.
  • the lower punch 303 was connected to the counter electrode and the reference electrode.
  • the impedance of the solid electrolyte material was measured at room temperature by an electrochemical impedance measurement method.
  • FIG. 3 is a graph showing a Core-Cole plot obtained by measuring the impedance of the solid electrolyte material of Example 1.
  • the real value of the impedance at the measurement point where the absolute value of the phase of the complex impedance is the smallest is regarded as the resistance value of the solid electrolyte material to the ionic conduction. See the arrow R SE shown in FIG. 3 for the real value.
  • the ionic conductivity was calculated based on the following mathematical formula (1).
  • ⁇ represents ionic conductivity.
  • S represents the contact area of the solid electrolyte material with the punch upper portion 301 (equal to the cross-sectional area of the hollow portion of the frame mold 302 in FIG. 2).
  • R SE represents the resistance value of the solid electrolyte material in impedance measurement.
  • t represents the thickness of the solid electrolyte material (that is, the thickness of the layer formed from the powder 101 of the solid electrolyte material in FIG. 2).
  • the ionic conductivity of the solid electrolyte material of Example 1 measured at 25 ° C. was 2.52 ⁇ 10 -3 S / cm. The measurement results are shown in Table 1.
  • FIG. 4 is a graph showing an X-ray diffraction pattern of the solid electrolyte material of Example 1.
  • the X-ray diffraction pattern of the solid electrolyte material of Example 1 was measured by the ⁇ -2 ⁇ method using an X-ray diffractometer (Rigaku, MiniFlex600) in a dry environment having a dew point of ⁇ 50 ° C. or lower.
  • Cu-K ⁇ rays (wavelengths 1.5405 ⁇ and 1.5444 ⁇ ) were used as the X-ray source.
  • the solid electrolyte material of Example 1 had a first crystal phase (that is, a trigonal crystal).
  • the diffraction peak having the highest intensity (that is, the strongest peak) in the X-ray diffraction pattern exists in the range of 29.0 ° or more and 32.0 ° or less, and the full width at half maximum of the strongest peak is 0.16 °. rice field.
  • the observed X-ray diffraction peak angle and the full width at half maximum of the strongest peak are shown in Table 2.
  • the solid electrolyte material (80 mg) of Example 1 and the above mixture (10 mg) were laminated in this order in an insulating cylinder having an inner diameter of 9.5 mm.
  • a pressure of 720 MPa was applied to the obtained laminate to form a solid electrolyte layer formed from the solid electrolyte material of Example 1 and a first electrode formed from the above mixture.
  • the solid electrolyte layer had a thickness of 400 ⁇ m.
  • the metal In (thickness: 200 ⁇ m), the metal Li (thickness: 200 ⁇ m), and the metal In (thickness: 200 ⁇ m) were laminated in this order on the solid electrolyte layer.
  • a pressure of 80 MPa was applied to the obtained laminate to form a second electrode.
  • a current collector made of stainless steel was attached to the first electrode and the second electrode, and a current collector lead was attached to the current collector.
  • Example 1 the battery of Example 1 was obtained.
  • FIG. 6 is a graph showing the initial discharge characteristics of the battery of Example 1. The initial charge / discharge characteristics were measured by the following method.
  • Example 1 The battery of Example 1 was placed in a constant temperature bath at 25 ° C.
  • Example 1 The battery of Example 1 was charged until a voltage of 3.68 V was reached at a current density of 76 ⁇ A / cm 2. The current density corresponds to a 0.05 C rate.
  • Example 2 Next, the battery of Example 1 was discharged until a voltage of 1.88 V was reached at a current density of 76 ⁇ A / cm 2.
  • the battery of Example 1 had an initial discharge capacity of 1.02 mAh.
  • Example 2 (Preparation of solid electrolyte material)
  • LiBr, LiCl, CaBr 2 , GdCl 3 , and SmCl 3 are used as raw material powders
  • LiBr: LiCl: CaBr 2 : GdCl 3 : SmCl 3 2.8: 1: 0.1: 0.7. : Prepared to have a molar ratio of 0.3.
  • compositions of the solid electrolyte materials of Examples 2 to 26, the values corresponding to a, b, c, and d of the composition formula (1), and the element species of M1 are shown in Table 1.
  • FIG. 4 shows the X-ray diffraction patterns of the solid electrolyte materials of Examples 2 to 9, 11, 12, 14 to 21, and 23 to 26.
  • the solid electrolyte materials of Examples 2 to 9, 11, 12, 14 to 21, and 23 to 26 all had a first crystal phase.
  • the strongest peaks of the solid electrolyte materials of Examples 2 to 9, 11, 12, 14 to 21, 23 to 26 were present in the range of 29.0 ° or more and 32.0 ° or less.
  • the observed X-ray diffraction peak angle and the full width at half maximum of the strongest peak are shown in Table 2.
  • broad peaks (halos) were further confirmed in the vicinity of 29.0 ° or more and 32.0 ° or less and in the vicinity of 14.0 ° or more and 18.0 ° or less, respectively. Therefore, it is probable that Example 26 contained an amorphous portion.
  • FIG. 5 shows the X-ray diffraction patterns of the solid electrolyte materials of Examples 10, 13, and 22.
  • the solid electrolyte materials of Examples 10, 13, and 22 all had a second crystal phase.
  • the solid electrolyte materials of Examples 13 and 22 had not only the second crystal phase but also the first crystal phase.
  • the strongest peak of the solid electrolyte material of Example 10 was present in the range of 24.0 ° or more and 35.0 ° or less.
  • the strongest peaks of the solid electrolyte materials of Examples 13 and 22 were present in the range of 12.0 ° or more and 16.0 ° or less.
  • the difference in the position of the strongest peak between Examples 10 and 13 and 22 is considered to be due to the difference in the orientation of the sample at the time of X-ray diffraction measurement.
  • the observed X-ray diffraction peak angle and the full width at half maximum of the strongest peak are shown in Table 3.
  • composition of the solid electrolyte materials of Comparative Examples 1 and 2 the values corresponding to a, b, c, and d of the composition formula (1), and the element species of M1 are shown in Table 1.
  • the solid electrolyte materials of Examples 1 to 26 had a lithium ion conductivity of 5.0 ⁇ 10 -5 S / cm or more near room temperature.
  • the solid electrolyte material is represented by the composition formula (1), and when M1 is contained, it is a solid as compared with the case where M1 is not contained.
  • the ionic conductivity of the electrolyte material was significantly improved. It is considered that this is because when the solid electrolyte material is represented by the composition formula (1) and contains M1, a pathway for diffusion of lithium ions is likely to be formed.
  • Examples 1 to 5 when the value of b is 0 or more and 0.7 or less, the ionic conductivity of the solid electrolyte material is improved. It is considered that this is because a pathway for diffusion of lithium ions is likely to be formed.
  • Examples 1 to 3 and 5 are compared with Example 4, when the value of b is 0 or more and 0.5 or less, the ionic conductivity of the solid electrolyte material is further improved. It is considered that this is because a pathway for diffusion of lithium ions is more likely to be formed.
  • Examples 1, 2, and 5 are compared with Example 3, when the value of b is 0 or more and 0.3 or less, the ionic conductivity of the solid electrolyte material is further improved. It is considered that this is because the path for the diffusion of lithium ions is more likely to be formed, and the width becomes optimum for ion conduction.
  • M1 is one selected from the group consisting of Mg, Ca, and Zn
  • the ionic conductivity of the solid electrolyte material is improved. It is considered that this is because a pathway for diffusion of lithium ions is likely to be formed.
  • M1 is Ca
  • the ionic conductivity of the solid electrolyte material is further improved. It is considered that this is because the route for diffusion of lithium ions is easily optimized.
  • Examples 9 and 15 to 20 when the value of a is larger than 0 and 0.5 or less, the ionic conductivity of the solid electrolyte material is improved. It is considered that this is because a pathway for diffusion of lithium ions is likely to be formed. As is clear when Examples 9 and 15 to 18 are compared with Examples 19 and 20, when the value of a is 0.025 or more and 0.2 or less, the ionic conductivity of the solid electrolyte material is further improved. rice field. It is considered that this is because the amount of lithium ions in the crystal is optimized.
  • Example 5 when the full width at half maximum of the strongest peak is 0.30 or less, the ionic conductivity of the solid electrolyte material is further improved. It is considered that this is because a pathway for diffusion of lithium ions is more likely to be formed.
  • the batteries of Examples 1 to 26 were all charged and discharged at room temperature.
  • the solid electrolyte material in which M1 is Sr or Ba in the composition formula (1) can be expected to have the same effect as the solid electrolyte material in the example in which M1 is Ca or Mg in the composition formula (1). This is because Sr and Ba are related to Ca and Mg as homologous elements.
  • the solid electrolyte material according to the present disclosure is a novel solid electrolyte material having lithium ion conductivity.
  • the solid electrolyte material according to the present disclosure is suitable for providing a battery that can be charged and discharged well.
  • the solid electrolyte material of the present disclosure is used, for example, in a battery (for example, an all-solid-state lithium ion secondary battery).

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Abstract

Un matériau d'électrolyte solide selon la présente invention comprend Li, M1, M2 et X. M1 est un élément choisi dans le groupe constitué par Mg, Ca, Sr, Ba et Zn. M2 est au moins un élément choisi dans le groupe constitué par Gd et Sm. X est au moins un élément choisi dans le groupe constitué par F, Cl, Br, et I. Une batterie (1000) selon la présente invention comprend une électrode positive (201), une électrode négative (203), et une couche d'électrolyte (202) disposée entre l'électrode positive (201) et l'électrode négative (203). Au moins un élément choisi dans le groupe constitué par l'électrode positive (201), l'électrode négative (203) et la couche d'électrolyte (202) contient le matériau d'électrolyte solide.
PCT/JP2021/019273 2020-07-22 2021-05-20 Matériau d'électrolyte solide et batterie l'utilisant WO2022018952A1 (fr)

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EP4001218A1 (fr) * 2020-11-12 2022-05-25 Samsung Electronics Co., Ltd. Composé conducteur d'ions solides, électrolyte solide comprenant celui-ci, cellule électrochimique comprenant celui-ci et son procédé de fabrication
US11735765B2 (en) 2021-01-08 2023-08-22 Samsung Electronics Co., Ltd. Solid ion conductor, solid electrolyte including the solid ion conductor, electrochemical device including the solid electrolyte, and method of preparing the solid ion conductor
US11961962B2 (en) 2020-07-02 2024-04-16 Samsung Electronics Co., Ltd. Solid ion conductor compound, solid electrolyte including the same, electrochemical cell including the same, and preparation method thereof

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US11961962B2 (en) 2020-07-02 2024-04-16 Samsung Electronics Co., Ltd. Solid ion conductor compound, solid electrolyte including the same, electrochemical cell including the same, and preparation method thereof
EP4001218A1 (fr) * 2020-11-12 2022-05-25 Samsung Electronics Co., Ltd. Composé conducteur d'ions solides, électrolyte solide comprenant celui-ci, cellule électrochimique comprenant celui-ci et son procédé de fabrication
US11735765B2 (en) 2021-01-08 2023-08-22 Samsung Electronics Co., Ltd. Solid ion conductor, solid electrolyte including the solid ion conductor, electrochemical device including the solid electrolyte, and method of preparing the solid ion conductor

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